Polyarlketone resin film and a laminate thereof with metal

ABSTRACT

A film of a resin composition comprising total 100 parts by weight of a crystalline polyarylketone resin (A) and a noncrystalline polyetherimide resin (B), and 5 to 50 parts by weight of a filler, said film satisfies the following relation
 
 Tc ( A )&lt; Tc ( A+B )≦ Tg ( B )+20
 
wherein, Tc (A) is a peak temperature of crystallization of the crystalline polyarylketone resin (A),Tc (A+B) is the peak temperature of crystallization of the film, and Tg (B) is a glass transition temperature of the noncrystalline polyetherimide resin (B), each temperature value being measured bu differential scanning calorimetry at a heating rate of 10 degrees C./minute. The film and a metal laminate thereof are suitable for electronics parts.

FIELD OF THE INVENTION

This invention relates to a polyarylketone resin film having an improvededge tearing resistance. The film is suitable for electronic parts suchas printed wiring boards. This invention relates also to a metallaminate comprising a metal body laminated on at least one side of thefilm.

DESCRIPTION OF THE PRIOR ART

A crystalline polyarylketone resin, typically polyetheretherketone, isexcellent in heat resistance, flame retardant property, hydrolysisresistance, and chemical resistance, and, therefore, widely used mainlyfor aircraft parts, electric parts or electronic parts. However, rawmaterials for the polyarylketone resin are very expensive. Further, aglass transition temperature of the resin is so low as about 140 degreesC. to 170 degrees C. For this reason, various attempts have been made tofurther improve heat resistance of the resin, among which a blend of theresin with a noncrystalline polyetherimide resin has attractedattentions. For instance, Japanese Patent Application Laid-open No.59-187054/1984 and National Publication of PCT Application No.61-500023/1986 disclose compositions of the crystalline polyarylketoneresin with the noncrystalline polyetherimide resin; Japanese PatentApplication Laid-open No. 59-115353/1984 describes that thosecompositions are useful for a substrate of a circuit board; JapanesePatent Application Laid-open No. 2000-38464 and Japanese PatentApplication Laid-open No. 2000-200950 by the present inventors disclosea printed wiring board comprising the aforesaid composition and aproduction method thereof.

A flexible printed wiring board made of a film of the composition of thecrystalline polyarylketone resin and the noncrystalline polyetherimideresin, which composition usually comprises an inorganic filler toimprove dimensional stability, is good in dimensional stability and heatresistance. However, its mechanical strength, especially edge tearingresistance, is not satisfactory, which results in poor foldingresistance or bending resistance. Therefore, reliable electricalconnection is not secured, and the board has only limited applications.Also, improvement is required in a handling property in a step ofprocessing the flexible printed wiring boards.

Thus, an object of the present invention is to provide a polyarylketoneresin film suitable as an electronic part, particularly having animproved edge tearing resistance and a metal laminate comprising thefilm laminated on a metal body.

SUMMARY OF THE INVENTION

The present inventors have found that the above problems can be solvedby using, as a major component, a resin composition comprising acrystalline polyarylketone resin having a specific crystallizationproperty and a noncrystalline polyetherimide resin.

Thus, the present invention is a film of a resin composition comprisingtotal 100 parts by weight of a crystalline polyarylketone resin (A) anda noncrystalline polyetherimide resin (B), and 5 to 50 parts by weightof a filler, said film having a peak temperature of crystallization, Tc(A+B) measured by differential scanning calorimetry at a heating rate of10 degrees C./minute, which satisfies the following relationTc(A)<Tc(A+B)≦Tg(B)−14.7wherein, Tc (A) is a peak temperature of crystallization of thecrystalline polyarylketone resin (A), Tc (A+B) is the peak temperatureof crystallization of the film, and Tg (B) is a glass transitiontemperature of the noncrystalline polyetherimide resin (B), eachtemperature value being measured by differential scanning calorimetry ata heating rate of 10 degrees C./minute.

The preferred embodiments of the present invention are as follows.

The film according to the film described above, wherein the crystallinepolyarylketone resin (A) is composed mainly of a polyetheretherketoneresin having structural repeating units of the formula (1) and thenoncrystalline polyetherimide resin (B) is composed mainly of apolyetherimide resin having structural repeating units of the formula(2).

The film according to any one of the films described above, wherein thefiller is an inorganic filler in an amount of from 10 to 40 parts byweight per total 100 parts by weight of the crystalline polyarylketoneresin (A) and the noncrystalline polyetherimide resin (B).

The film according to any one of the films described above, wherein themelting peak temperature of crystals of a mixed resin consisting of thecrystalline polyarylketone resin (A) and the noncrystallinepolyetherimide resin (B) is 260 degrees C. or higher, and a mixing ratioof (A)/(B) is in a range of from 70/30 to 30/70.

Another aspect of the present invention is a crystallized film from thefilm according to any one of described above. Preferred embodiments ofthe crystallized film are as follows.

The film according to the film described above, wherein thecrystallization is performed in an out-line crystallization method.

The film according to any one of the films described above, wherein thefilm has a coefficient of linear expansion of 30×10⁻⁶/degrees C. orsmaller and an edge tearing resistance of at least 45 N in bothlongitudinal and transverse directions.

Still another aspect of the present invention is a metal laminatecomprising a metal body laminated on at least one side of the filmaccording to any film described above without an adhesive layertherebetween.

Preferably, the metal comprises copper, aluminum, or stainless steal,and the metal body is laminated to the film by heat bonding.

The present invention relates also to a crystallized film comprisingtotal 100 parts by weight of a crystalline polyarylketone resin (A) anda noncrystalline polyetherimide resin (B), and 5 to 50 parts by weightof a filler, said film having a coefficient of linear expansion of30×10⁻⁶/degrees C. or smaller and an edge tearing resistance accordingto JIS C2151 of at least 50 MPa in both longitudinal and transversaldirections.

A metal laminate comprising a metal body laminated on the film describedabove is also provided. Preferably, the metal comprises copper,aluminum, or stainless steal

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present film is prepared from a composition comprising 100 parts byweight of a mixture of a crystalline polyarylketone resin (A), anoncrystalline polyetherimide resin (B), and 5 to 50 parts by weight ofa filler. The term “film” as used herein also implies a sheet having arelatively large thickness of about 500 μm or more.

The crystalline polyarylketone resin used in the present invention is athermoplastic resin having structural units bonds. Typical examples ofthe polyarylketone resin are polyether ketone, polyetheretherketone, andpolyetherketoneketone, among which the polyetheretherketone of thefollowing repeating unit (1) is preferably used in the presentinvention. The polyetheretherketone having the repeating unit isavailable under trade names, “PEEK151G”, “PEEK381G”, and “PEEK450G”,from VICTREX Co. The crystalline polyarylketone resin can be used aloneor in combination of two or more of them.

The noncrystalline polyetherimide resin is a thermoplastic resin havingstructural units which comprises aromatic nucleus bonds, ether bonds,and imide bonds. Examples of the noncrystalline polyetherimide resin arethose having the following repeating unit (2) or (3), which areavailable under a trade name, “Ultem CRS5001” and “Ultem1000”,respectively, from General Electric Co. In the present invention, anynoncrystalline polyetherimide resin may be used, as far as a mixturewith the crystalline polyarylketone resin below satisfies thecrystallization property described later in the specification. In thepresent invention, the polyetherimide resin having the followingrepeating unit (2) is preferably used. The reason for this may be that amixture of the polyetheretherketone of the formula(1) and thepolyetherimide resin of the formula (2) is different in electronicinteraction between molecules from that in a mixture of the resin(1) andthe polyetherimide resin of the formula (3), and also has differentmiscibility and, therefore, develops a unique high-order structure,which contributes to the improvement in edge tearing resistance.

The noncrystalline polyetherimide resin may be produced in any knownmethod. Usually, the noncrystalline polyetherimide resin of theaforesaid formula (2) is produced by a known method as apolycondensation product of 4,4′-[isopropylidenebis(p-phenyleneoxy)diphthalic dianhydride with p-phenylenediamine; andthe noncrystalline polyetherimide resin of the formula (3), as apolycondensation product of 4,4′-[isopropylidenebis(p-phenyleneoxy)diphthalic dianhydride with m-phenylenediamine. Theaforesaid noncrystalline polyetherimide resin(2) may include othercopolymerizable monomeric units in an amount which does not adverselyaffect the present invention. The noncrystalline polyetherimide resincan be used alone or in combination of two or more of them.

When the present film is used for a base material of an electronic boardsuch as a printed wiring board, it is preferred that a melting peaktemperature of crystals of a mixture of the crystalline polyarylketoneresin (A) and the noncrystalline polyetherimide resin (B) is 260 degreesC. or higher, and a weight ratio of the polyarylketone resin (A) to thenoncrystalline polyetherimide resin (B) is in the range of fromA/B=70/30 to 30/70.

If the amount of the crystalline polyarylketone resin is more than 70 wt% or the amount of the noncrystalline polyetherimide resin is less than30 wt %, an increase in glass transition temperature of the whole mixedresin is less, so that heat resistance tends to be undesirably low. Inaddition, a volume shrinkage (dimensional change) associated with thecrystallization is larger, so that reliability of a circuit board tendsto be undesirably poor.

If the amount of the crystalline polyarylketone resin is less than 30 wt% or the amount of the noncrystalline polyetherimide resin is more than70 wt %, a degree and rate of crystallization of the resin mixture areso small that soldering heat resistance is undesirably low even whenpeak melting temperature of crystal is 260 degrees C. or higher.

Therefore, in the present invention, the composition comprising 65 to 35wt % of the aforesaid crystalline polyarylketone resin and 35 to 65 wt %of the noncrystalline polyetherimide resin is preferably used as a basematerial of electronic boards.

If a filler is incorporated in an amount of more than 50 parts by weightper 100 parts by weight of the aforesaid resin composition, flexibilityand edge tearing resistance of a film are undesirably lower. If thefiller is incorporated in an amount of less than 5 parts by weight,improvement in dimension stability through decrease in a coefficient oflinear expansion is undesirably smaller. Therefore, the filler isincorporated preferably in an amount of from 10 to 40 parts by weightper 100 parts by weight of the aforesaid resin composition. For anapplication where balance between the dimension stability and theflexibility or the edge tearing resistance is important, the amount ofthe filler is adjusted preferably in a range of from 20 to 35 parts byweight.

Any known filler can be used, for example, inorganic filler such astalc, mica, clay, glass, aluminum, silica, aluminum nitride, and siliconnitride, and fiber such as glass fiber and aramid fiber. These may beused alone or in combination of two or more of them. The filler may besurface treated with coupling agents such as titanate, fatty acids,resin acids, or various kinds of surfactants. Particularly when thepresent film is used for a printed wiring board, inorganic filler havingan average particle size of from 1 to 20 μm and an average aspect ratio,i.e., a ratio of a particle diameter to thickness, of about 20 to about30 or larger, particularly 50 or larger, is preferably used.

The present film is characterized in that it comprises the aforesaidresin composition and has a peak temperature of the crystallization, Tc(A+B), measured by differential scanning calorimetry at a heating rateof 10 degrees C./minute satisfies the following relation (I).Tc(A)<Tc(A+B)≦Tg(B)+20  (I)

In the relation (I), each value in degrees C. is determined bydifferential scanning calorimetry at a heating rate of 10 degreesC./minute, wherein Tc (A) is a peak temperature of the crystallizationof the crystalline polyarylketone resin (A) alone, Tc (A+B) is a peaktemperature of crystallization of the film of the present invention, andTg (B) is a glass transition temperature of a film of the noncrystallinepolyetherimide resin (B) alone.

If Tc (A+B) is higher than [Tg (B)+20], that is, if a crystallizationtemperature of a film exceeds a glass transition temperature of a filmof the noncrystalline polyetherimide resin (B) alone plus 20 degrees C.,a greater decrease in edge tearing resistance may be caused bycrystallization treatment, so that reliability of circuit and thehandling property of the film may tend to be worsen, which isundesirable. It is believed without intention to limit the inventionthat molecules of the noncrystalline polyetherimide resin (B) movevigorously before the crystallization of the film is completed, whichallows a crystalline structure such as spherulites originating from thecrystalline portion of the polyarylketone resin (A) to highly develop,and then the interface between the spherulites acts as a defect todegrade the edge tearing resistance.

If Tc (A+B) equals Tc (A), that is, if the peak temperature of thecrystallization of the present film equals the peak temperature of anamorphous film of the crystalline polyarylketone resin (A) alone,compatibility between the resin (A) and the resin (B) is bad, so thatmechanical properties and appearance of the film tends to be bad.Therefore, the Tc (A+B) is preferably in a range of from [Tc (A)+5]degrees C. to [Tg (B)+15] degrees C., particularly from [Tc (A)+10]degrees C. to Tg (B).

By crystallizing the aforesaid film, its heat resistance can beimproved. A degree of the crystallization can be monitored, forinstance, by a value, (ΔHm−ΔHc)/ΔHm, determined by differential scanningcalorimetry. In the present invention, the degree of crystallization issuch that the value satisfies the following relation (II).0.90≦[(ΔHm−ΔHc)/ΔHm]  (II)wherein, ΔHm is a heat of crystal fusion in J/g and ΔHc is a heat ofcrystallization during the heating in J/g. The maximum of the value is1.0. The greater the value, the greater the degree of crystallization.If the value is less than 0.90, dimension stability and/or heatresistance of the film-may not be undesirably insufficient.

In the present invention, a heat of crystal fusion in J/g,ΔHm, and aheat of crystallization in J/g, ΔHc(J/g), are determined from athermogram obtained by heating 10 mg of a sample from room temperatureto 400 degrees C. at a heating rate of 10 degrees C./minute according tothe Japanese Industrial Standards, JIS-K7122, using DSC-7, exPerkin-Elmar Inc.

The aforesaid value, [(ΔHm−ΔHc)/ΔHm], depends more on molding andprocessing conditions of the film than a type and molecular weights ofthe raw material polymers, and contents in the composition. By cooling afilm immediately after molding the molten raw polymers, a film having asmaller value can be obtained. Subjecting the film to crystallizationtreatment can increase the value.

Any method and a period of time can be employed for the crystallizationtreatment, such as a cast crystallization method where a film iscrystallized when cast-extruded; an in-line crystallization method wherecrystallization is effected in a film molding line, e.g., on a heattreatment roll or in a hot wind furnace; and an out-line crystallizationmethod where crystallization is effected off a film molding line, e.g.,in a thermostatted oven or by a hot press.

In the present invention, the out-line crystallization method ispreferably used in view of stability of production and uniformity ofproperty. A time of the crystallization treatment may be long enough forthe value in the relation (II) to be 0.9 or higher, and may be in arange of from a few seconds to a few tens hours, preferably from a fewminutes to about 3 hours.

The present film after crystallization treatment has a coefficient oflinear expansion of 30×10⁻⁶/degrees C. or smaller and an edge tearingresistance of at least 45 N, preferably at least 56.3 N, in bothlongitudinal and transversal directions. The film is particularlysuitable for a base material of an electronic board such as a flexibleprinted wiring board.

If the coefficient of linear expansion is larger than 30×10⁻⁶/degreesC., a laminate of a film with a metal foil tends to curl or warp or tohave insufficient dimension stability. A preferred range of thecoefficient of linear expansion depends on a type of the metal foilused, a circuit pattern formed on the front and the back sides of thelaminate, and the laminate structure, but is generally from10×10⁻⁶/degrees C. to 25×10⁻⁶/degrees C. If the edge tearing resistanceis smaller than 40 MPa, reliability of circuit connection isinsufficient in a thin board such as a flexible printed wiring board, ora handling property during processing of the board tends to be bad. Inthe present invention, the edge tearing resistance is measured accordingto edge tearing resistance test specified in JIS C2151, where a testspecimen of 15 mm width by 300 mm length was cut out from a 75 μm-thickfilm and tested at a drawing speed of 500 mm/min using a test fixture B.

The present composition may comprise other resin or various additives inaddition to inorganic fillers, such as heat stabilizers, UV absorbers,photo-stabilizers, nucleating agents, colorants, lubricants, and flameretardants in such an amount that does not adversely affect theproperties of the composition.

To mix additives, any known method can be used. For example, (a) amaster batch is prepared by incorporating the additive at a highconcentration, typically of from 10 to 60 wt %, in an appropriate baseresin, the polyarylketone resin and/or the noncrystalline polyetherimideresin, and added to the resins to be used to attain a desiredconcentration of the additive and then mechanically blended with akneader or an extruder, or (b) the additive is mechanically blendeddirectly with the resins to be used in a kneader or an extruder. Amongthe aforesaid mixing methods, the method (a), preparing a master batchand blending, is preferred because higher dispersion and easier handlingof the additives is attained. To improve handling property of the film,embossing or corona treatment may be applied to a surface of the film.

The present film may be formed by any known method such as an extrusioncasting method using a T-die and a calendar method. Preferably, theextrusion casting method using a T-die is used, but not limited to it,because it allows one to make a film with ease and stable productivity.In the extrusion casting method using a T-die, a molding temperature isgenerally in a range of from about a melting temperature of thecomposition to about 430 degrees C., though it is adjusted depending ona flow property and film moldability of the composition. The filmusually has a thickness of from about 10 to about 800 μm.

Another aspect of the present invention is a metal laminate comprising ametal body laminated on at least one side of the aforesaid film withoutan adhesive layer therebetween. The laminate can be obtained by heatbonding a metal body on one side of a film, for example, a film thatsatisfies the relation (I). During the heat bonding, pressure may beapplied. Preferably, the film is used having the value, [(ΔHm−ΔHc)/ΔHm],of 0.5 or lower. If the value is larger than 0.5, the lamination withthe metal body needs to be performed at a higher temperature. Inaddition, multilayer lamination may be difficult. After laminating themetal on the film, the film may be subjected to the crystallizationtreatment to increase the value, [(ΔHm−ΔHc)/ΔHm], to 0.9 or higher tothereby improve the heat resistance of the laminate.

Any known methods can be used to heat bonding a metal body on a filmwithout an adhesive layer therebetween, for example, a method ofpressing a film and a metal body in a press preheated to a desired heatbonding temperature, a method of preheating a metal body to a heatbonding temperature and pressing it onto a film, a continuous method ofpressing a film and a metal body on a hot rolls preheated to a heatbonding temperature, and a combination thereof. When a press is used, itis preferred to employ a pressure per area of from 0.98 to 9.8MPa,i.e.,10 to 100 kg/cm², under a reduced pressure of about 973 hPa soas to avoid oxidation of the metal. The lamination may be made on onesides of the film and the metal, or on both sides of the film and/or themetal.

Any known method such as etching may be used to form conductive circuitson the metal body of the present metal laminate for an electronic boardsuch as a flexible printed wiring board, rigid-flexible board, built-upmultilayer board, bundled multilayer board, and metallic base board.Methods to form interlayer connection in a multilayer board includeplating through-holes with copper, filling a conductive paste or solderballs in through-holes or inner via holes, and utilizing ananisotropically conductive material comprising fine conductive particlesin an insulating layer.

The metal body to be used in the present invention may comprise copper,silver, gold, iron, zinc, aluminum, magnesium, nickel, or alloysthereof. These may be used alone or in a mixture of two or more of them.Also, the metal may be surface treated with a surface treatment agentsuch as aminosilane, as far as the purpose of the present invention isnot disturbed.

The metal body may be in a form of a structural element, a strip to formelectric or electronic circuit, or a foil having a thickness of fromabout 3 μm to about 70 μm to form circuit thereon by etching. Analuminum plate or foil is preferred mostly for heat dissipation;stainless steal plate or foil is preferred for an application where highcorrosion resistance, mechanical strength, or electric resistance isrequired; a copper foil is preferred for forming a complicated and finecircuit. Particularly one which is chemically treated, e.g., by blackoxidation treatment is preferred. To increase bonding strength, asurface of the metal body to be bonded to a molded article of the mixedresin is preferably roughened chemically or mechanically before bonded.An example of such a roughened conductive film is a roughened copperfoil which has been electrochemically treated in the production ofelectrolytic copper foils.

EXAMPLES

The present invention will be explained with reference to the followingExamples, but not limited to them. Measurements and evaluation of thefilms described in the Examples were carried out as follows, wherein alongitudinal direction means a machine direction of an extruder and atransversal direction means a direction normal to the machine direction.

(1) Glass Transition Temperature (Tg), Peak Temperature ofCrystallization (Tc), Melting Peak Temperature of Crystals (Tm)

These temperatures were determined from a thermogram obtained by heating10 mg of a sample at a heating rate of 10 degrees C./minute according tothe Japanese Industrial Standards, JIS-K7121, using DSC-7, exPerkin-Elmer Inc.

(2) (ΔHm−ΔHc)/ΔHm

The value, (ΔHm−ΔHc)/ΔHm, was calculated from a heat of crystal fusion,ΔHm(J/g), and a heat of crystallization, ΔHc(J/g), which were determinedfrom a thermogram obtained by heating 10 mg of a sample at a heatingrate of 10 degrees C./minute according to JIS-K7122, using DSC-7, exPerkin-Elmer Inc.

(3) Coefficient of Linear Expansion

Using thermomechanical analyzer (TMA), model SS6100, ex Seiko InstrumentCorp., a test strip having a 10 mm length and a cross-sectional area of1 mm² cut out from a film was fixed under a tensile load of 9.807×10⁻⁴ Nand heated from 30 degrees C. to 220 degrees C. at a heating rate of 5degrees C./minute. A coefficients of thermal expansion in longitudinaldirection, α1(long.), and transversal direction, α1(trans.), weredetermined by measuring expanded amounts versus temperature.

(4) Edge Tearing Resistance

According to the edge tearing resistance test specified in JIS C2151, atest specimen of 15 mm width by 300 mm length was cut out from a 75μm-thick film and tested both in its longitudinal and transversaldirections at a drawing speed of 500 mm/min using a test fixture B.

(5) Bonding Strength

The bonding strength was measured according to the method for measuringpeeling strength of a film in its original state specified in JIS C6481.

(6) Soldering Heat Resistance

In accordance with JIS C6481 for the soldering heat resistance test of afilm in its original state, a test specimen was floated on a solder bathat 260 degrees C. for 20 seconds in such a manner that a copper foillaminated on the film was in contact with the solder. After cooled toroom temperature, the specimen was visually observed for the presence ofblistering and/or peeling and evaluated.

Example 1

As shown in Table 1, a composition consisting of 70 parts by weight of apolyetheretherketone resin (PEEK381G, ex Victrex Co., having a Tg of 143degrees C., Tc of 169 degrees C., and Tm of 334 degrees C., hereinafterreferred to as PEEK), 30 parts by weight of a polyetherimide resin(Ultem-CRS5001, ex General Electric Co., having a Tg of 226 degrees C.,hereinafter referred to as PEI-1), and 25 parts by weight of acommercially available mica(having an average particle size of 10 μm andan average aspect ratio of 50) was melt kneaded at 380 degrees C. in anextruder provided with a T-die, and molded into a film of 75μm-thickness, which was rapidly cooled on cast rolls at 160 degrees C.The film obtained is hereinafter referred to as amorphous film. Then,the film obtained was subjected to crystallization treatment in athermostatted oven at 230 degrees C. for 180 minutes. The crystallizedfilm thus obtained is hereinafter referred to as crystallized film. Theamorphous film and the crystallized film were analyzed for thermalproperties and edge tearing resistance. The results are as seen in Table1.

Example 2

The procedures of Example 1 were repeated except that the mixing ratioof PEEK to PEI-1 was changed to 40 parts by weight to 60 parts by weightas seen in Table 1. As in Example 1, an amorphous film and acrystallized film were obtained. The resistance and so on are as seen inTable 1.

Example 3

The procedures of Example 1 were repeated except that the mixing ratioof PEEK to PEI-1 was changed to 30 parts by weight to 70 parts by weightas seen in Table 1. As in Example 1, a noncrystalline film and acrystallized film were obtained. The results of the measurements ofthermal properties, edge tearing resistance and so on are as seen inTable 1.

Comparative Example 1

The procedures of Example 1 were repeated except that a noncrystallinepolyetherimide resin (Ultem 1000, ex General Electric Co., having a Tgof 216 degrees C., hereinafter simply referred to as PEI-2) was usedinstead of PEI-I as seen in Table 1. As in Example 1, an amorphous filmand a crystallized film were obtained. The results of the measurementsof thermal properties, edge tearing resistance and so on are as seen inTable 1.

Comparative Example 2

The procedures of Example 2 were repeated except that PEI-2 was usedinstead of PEI-1 as seen in Table 1. As in Example 1, an amorphous filmand a crystallized film were obtained. The results of the measurementsof thermal properties, edge tearing resistance and so on are as seen inTable 1.

Comparative Example 3

The procedures of Example 3 were repeated except that PEI-2 was usedinstead of PEI-1. As in Example 3, an amorphous film and a crystallizedfilm were obtained. The results of the measurements of thermalproperties, edge tearing resistance and so on are as seen in Table 1.

Example 4

A composition consisting of 40 parts by weight of PEEK, 60 parts byweight of PEI-1 and 30 parts by weight of mica used in Example 1 wasextruded at 380 degrees C. into a 75 μm-thick film in an extruderprovided with a T-die. Immediately after extruded, a copper foil of athickness of 18 μm with a roughened surface was laminated on one side ofthe extruded film on a casting roll at 250 degrees C., whereby a copperfoil laminate was obtained. A test piece having a size of A4 was cut outfrom the laminate. After forming a desired circuit on it by etching,through-holes were drilled, into which a conductive paste was filled.Then, two sheets of the laminates thus obtained with the conductivepaste being filled in the through-holes were stacked on an aluminumplate of 1 mm thickness in he order of an aluminum plate/resinfilm/copper foil/resin film/copper foil, which were vacuum pressed at apressure of 2.94 MPa at 240 degrees C. for 30 minutes into an aluminumbased multilayered laminate. The aluminum based multilayered laminatethus obtained showed no warp, an adhesion strength of the copper foil of1.6 N/mm and a good solder heat resistance.

TABLE 1 Example Comparative Example 1 2 3 1 2 3 PEEK, parts by weight 7040 30 70 40 30 PEI-1, parts by weight 30 60 70 PEI-2, parts by weight 3060 70 Mica, parts by weight 25 25 25 25 25 25 Crystallization Propertiesof the Amorphous Film Crystallization Temperature of Resin CompositionTc(A + B), ° C. 194.6 211.3 210.0 205.1 247.3 258.3 Tg of PEI usedTg(B), ° C. 226 226 226 216 216 216 Evaluation of the Crystallized FilmCrystallization Temperature, ° C. 230 230 230 230 260 260Crystallization Time, minute 180 180 180 180 180 180 (ΔHm − ΔHc)/ΔHm (−)0.99 or 0.99 or 0.99 or 0.99 or 0.99 or 0.99 or greater greater greatergreater greater greater Coefficient of Linear Expansion α1(longitudinal)10⁻⁶/° C. 17 14 13 21 19 18 Coefficient of Linear Expansionα1(transversal) 25 21 18 28 27 25 Edge Tearing Resistance, Nlongitudinal 216.3 204.5 194.3 150.1 144.2 133.9 transversal 119.3 98.680.9 51.4 33.9 26.6

It can be seen from Table 1 that the films of Examples 1 to 3 having thecrystallization properties specified in the present invention had wellbalanced properties between the dimension stability and the edge tearingresistance. The metal laminate of Example 4 obtained by heat bonding thefilm having the crystallization properties specified in the presentinvention was found to have excellent adhesion strength and solder heatresistance. On the other hand, the films of Comparative Examples 1 to 3of which crystallization properties were outside the scope of thepresent invention showed poorer edge tearing resistance.

INDUSTRIAL APPLICABILITY

The present film has an excellent edge tearing resistance. The film andthe metal laminate thereof are suitable for electronic parts. dimensionstability and the edge tearing resistance. The metal laminate of Example5 obtained by heat bonding the film having the crystallizationproperties specified in the present invention was found to haveexcellent adhesion strength and solder heat resistance. On the otherhand, the films of Comparative Examples 1 and 2 of which crystallizationproperties were outside the scope of the present invention showed pooreredge tearing resistance.

1. A film of a resin composition comprising total 100 parts by weight ofa crystalline polyarylketone resin (A) and a noncrystallinepolyetherimide resin (B), and 5 to 50 parts by weight of a filler, saidfilm having a peak temperature of crystallization, Tc (A+B), measured bydifferential scanning calorimetry at a heating rate of 10 degreesC./minute, which satisfies the following relationTc(A)<Tc(A+B)≦Tg(B)−14.7 wherein, Tc (A) is a peak temperature ofcrystallization of the crystalline polyarylketone resin (A), Tc (A+B) isthe peak temperature of crystallization of the film, and Tg (B) is aglass transition temperature of the noncrystalline polyetherimide resin(B), each temperature value being measured by differential scanningcalorimetry at a heating rate of 10 degrees C./minute.
 2. The filmaccording to claim 1, wherein the crystalline polyarylketone resin (A)comprises a polyetheretherketone resin having structural repeating unitsof formula (1) and the noncrystalline polyetherimide resin (B) comprisesa polyetherimide resin having structural repeating units of formula (2)


3. The film according to claim 1, wherein the filler is an inorganicfiller in an amount of from 10 to 40 parts by weight per total 100 partsby weight of the crystalline polyarylketone resin (A) and thenoncrystalline polyetherimide resin (B).
 4. The film according to claim2, wherein the melting peak temperature of crystals of a mixed resinconsisting of the crystalline polyarylketone resin (A) and thenoncrystalline polyetherimide resin (B) is 260 degrees C. or higher, anda mixing ratio of (A)/(B) is in a range of from 70/30 to 30/70.
 5. Acrystallized film from the film according to claim
 1. 6. The filmaccording to claim 5, wherein the crystallization is performed in anout—line crystallization method.
 7. The film according to claim 5,wherein the film has a coefficient of linear expansion of 30×10⁻⁶/degrees C. or smaller and an edge tearing resistance of at least56.3 N in both longitudinal and transversal directions.
 8. A metallaminate comprising a metal body laminated on at least one side of thefilm according to claim 1 without an adhesive layer therebetween.
 9. Themetal laminate according to claim 8, wherein the metal body comprisescopper, aluminum, or stainless steel.
 10. The metal laminate accordingto claim 8, wherein the metal body is laminated to the film by heatbonding.
 11. A crystallized film comprising total 100 parts by weight ofa crystalline polyaryilketone resin (A) and a noncrystallinepolyetherimide resin (B), and 5 to 50 parts by weight of a filler, saidfilm having a coefficient of linear expansion of 30 ×10⁻⁶/degrees C. orsmaller and an edge tearing resistance of at least 56.3 N in bothlongitudinal and transversal directions.
 12. A metal laminate comprisinga metal body laminated on the film according to claim
 11. 13. The metallaminate according to claim 12, wherein the metal body comprises copper,aluminum, or stainless steel.